Diethyl (cyanomethyl)phosphonate → tert-Butyl 4-(cyanomethylidene)piperidine-1-carboxylate

HRID 500280ノート

反応式

HRID 500280 の反応式
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].O=[C:19]1[CH2:24][CH2:23][N:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:21][CH2:20]1>C1COCC1>[C:7]([CH:9]=[C:19]1[CH2:24][CH2:23][N:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:21][CH2:20]1)#[N:8]

参加物

5

反応物 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 15326949tert-Butyl 4-(cyanomethylidene)piperidine-1-carboxylate収率 97.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To a solution of 1.0 M of potassium tert-butoxide in THF (26.3 mL) at 0° C. was added drop wise a solution of diethyl cyanomethylphosphonate (4.47 mL, 0.0276 mol) in THF (33.6 mL). The reaction was warmed to RT and then cooled at 0° C. again. To the reaction mixture was then added a solution of tert-butyl 4-oxo-1-piperidinecarboxylate (5.0 g, 0.025 mol) in THF (6.72 mL). The reaction was allowed to warm up to RT and stirred overnight. After being quenched with water, the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried, and concentrated. The crude mixture was purified on silica gel eluting with EtOAc in hexanes (0-60%) to give the desired product (5.4 g, 96.81%). LCMS: (M+Na)=244.9, (M-56+H)=167.0.

後処理

  1. temperaturecooled at 0° C. again
  2. temperatureto warm up to RT
  3. customAfter being quenched with water
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. customdried
  7. concentrationconcentrated
  8. customThe crude mixture was purified on silica gel eluting with EtOAc in hexanes (0-60%)

出典と根拠

ORDレコード
ord-3c76746be00f41c4990bb200bd33ec3f
出典データセット
uspto-grants-2010_08
特許番号
US07767675B2

反応ノート

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